New azo dyestuffs



Patented Oct. 1, 1929 PATENT OFFICE WINFRID HENTRICH AND MAX HARD'IMANN,OF WIESDORF-ON-THE-RHINE, GER- MANY, ASSIGNORS TO GENERAL ANILINE WORKS,

CORPORATION 01 DELAWARE No Drawing. Application filed July 2,

Our invention 'relatesto new tetrakisazodyestuffs of the generalformula:

OX OH SOaH wherein R, and R represent aromatic resi-. dues, R,represents a residue of the na ththalene series, B, a residue of anysuita le' end component, X hydrogen, an a kyl or acidyl group, and Yhydrogen or any monovalent substituent.

They are obtainable, for instance, by diazotizing a disazo compound ofthe general formula:

wherein R, represents an aromatic residue, R,- a residue of thenaphthalene series, and X hydrogen, an alkyl. or acidyl group, couplingthe diazo compound thus obtained with a compound of the general formula8 05K NH.CO.Rr-NH3 wherein R represents an aromatic residue and Yhydrogen or a monovalent substituent, diazotizing again, and couplingwith any suitable end component.

For the end component one may use for instance salicylic acid,o-cresotinic acid,

1.3-dihydroxyquinoline, a pyrazolone-compound, a methyl-ketol compoundetc.

The new dyestufis dye cotton clear green shades of excellent fastness tolight. They are in a dry state dark powders of grayishgreen toblack-green to black color, easily soluble in water with a blue-green toyellowgreen color, easily soluble in concentrated sulfuric acid witholive-green color.

INQ, OF NEW YORK, N. 'Y., A.

NEW AZO DYESTUFF'S 1927, Serial No. 208,266, and in Germany my 16, 1926.

The following examples serve to illustrate our invention Withoutlimiting it thereto:

N=N NH:

, oumms are stirred with a small amount of water to a paste. Whilecooling well, 280 parts by volume of caustic soda lye of 38 B. areadded. After the dyestufl' is completely dissolved, an aqueouswell-cooled solution of 70 parts of sodium nitrite is slowly introduced,and then 1400 to 2000 parts by volume of well-cooled hydrochloric acidof 20% strength are added at once. The diazotation takes place quickly.After addition of com mon 'salt the diazocompound separates as aviolet-brown precipitate. It is filtered oif while cold and slowlyintroduced into a wellstirred and fromoutside cooled solution of 358parts 4 aminobenzoyl-2-amino-5-hydroxy-naphthalene-7=sulfonic acid in100 parts by volume of ice-Water, a small amount of ammonia-water and2000 parts by volume of technical pyridine. The coupling process takesplace at once, while the solution becomes blue-black. The dyestufi issalted out and filtered. After being purified by recrystallizing it isdissolved in warm water, the solution is cooled to a temperature of '0to +5 (1.; an aqueous solution of 70-parts .of sodium nitrite isintroduced and the mixture is acidified by adding about 800 parts byvolume of hydrochloric acid of 20% strength. After addition of commonsalt the diazotrisazo-compound separates as a blackviolet precipitate ofmetallic lustre. It is 100 with a sulfonating agent, in 300 parts by Thereaction takes place volume of water. quickly. The dyestutl is saltedout, filtered, pressed and dried. It is easily soluble in water and dyescotton clear green shades of excellent fastness to light. It correspondsto the formula no.5 N=N Dyestufi's of similar shades and the sameproperties as to fastness can be obtained by using:

1. Instead of l-aminobenzene-2 .5-disulfonic acid2-amino-1-methoxybenzene-4-sulfonic acid,3-chloro-1-amin0benzene-6-sulfonic acid, 1-aminobenzene-3-sulfonic acid,1-aminobenzene-2.4-disulfonic acid, 4-nitro-1-aminobenzene-2.5-disulfonic acid, 5-sulfonic acid-2-aminobenzoic acid,aniline and its substitution products.

2. Instead of 1-aminonaphthalene-7-sulfonic acid used in the aboveexample in the second place one can use l-aminonaphthalenefi-sulfonicacid, a mixture of isomeric sulfonic acids or l-aminonaphthalene.

3. In the third place one may use instead ofl-amino-2-ethoxynaphthalene-6-sulfonic acidl-amino-2-methoxynaphthalene, l-amino-2.7-dimethoxynaphthalene,1-amino-2- naphthydroxy-fl-propionic acid of the formula NH the1-amino-2.7-naphthyleneglycolic acid of formula OOOBZCHz. .0311] 003.

or the co-SlllfOIliC acid ester of 1-amino-2 1-amino-2-naphthydroxy--propionic acid can be prepared by condensation of 2-hydroxynaphthalenewith ,B-chloropropionic acid, mono-nitration of, the condensationproduct and reduction.

The new product thus prepared represents a crystalline reddish powderforming a hydrochloric acid salt easily soluble in water.

1-amino-2.7-naphthyleneglycolic acid can be prepared by condensation of2.7-dihydroxynaphthalene with 2 molecular proportions ofmono-chloro-acetic acid, mono-nitra tion of this condensation productand reduc tion. I

The substance thus obtained represents a grey-brownish crystallinepowder easily soluble in sodium carbonate.

1-amino-2-hydroxy-ethoxynaphthalene can be prepared by nitration andfollowing reduction of w-SlllfOIliO acid ester of the hydroxyethyletherof 2-hydroxy-naphthalene described in the German Letters Patent No.443,340. I

The new product thus obtained represents an almost colourlesscrystalline powder easily soluble in sodium carbonate.

The dyestufl's thus obtained have clear green shades of excellentfastness to light and according to the components used possess a blue toyellow hue.

4. Instead of amino-benzoyl-2-amino-5- hydroxynaphthalene-7-sulfonicacid one can use in the fourth place other derivatives of2-amino-5-hydroxynaphthalene-7-sulfonic acid, for instance thederivative substituted in the 1-position, which contain in heteronuclearside-chains diazotizable amino-groups, for instance 4'- (or 3-)aniinobenzoyl-Q-amino-5-hydroxynaphthalene-1.7- or 3.7-disulfonic acids,or 4- (or. 3-) aminobenzoyl-2-amino-lchloro-5-hydroxynaphthalene7-sulfon-= ic acid, or4"-aminobenzoyl-4'-aminobenzcyl-2-amino-5-l1ydroxynaphthalene-7-sulfonic acid, or an isomer thereof, or3'-aminophenyl- 1.2 naphthimidazole 5 hydroxy 7 sulfonic acid, or 4'-(or 3'-) aminophenyl-L2-naphthothioazole-5-hydroxy=7-sulfonic acid, orthe corresponding triazole derivatives or 3-ami- DO-y-(5-hydroxy-7-sulfonic acid-2-naphthyl) -benzimidazole (which can beprepared by heating 2'-4'-diaminophenyl-2-amino-5- naphthol-7-sulfonicacid with formic acid,-

and heatin the m-formyl-amino- -5-hydroxy-7-sul omcacid-2-naphthylbenzimidazol in mineral acid solution to form the freeamino comppund and which corresponds to the most pro able formula: v

[ITO-NH:

or 4- (or 3'-) -aminophenyl-2- (5-hydroxy-7- sulfonic acid)-naphthylurea' of the formula:

no. imconmctmnm -azone (salicylic acid, o-cresotinic acid, 2A0

corresponding to the probable formula:

and being obtainablefrom o-amino-benzenesulfoacetic acidof the. formula:

by splitting off one molecule of water.

Dihydroxyquinoline of the probable formula:

are diazotized as described in Example 1. The suspension of thediazodisazo compound thus obtained is slowly introduced to an outsidewell-cooled solution of 355 arts 3'-aminophenyl-1.2-naphthimidazole-5-hydroxy-7-sulfonic acid in 100 parts by volume of ice-water, 500 partsby volume of ammonia water of 20% strength and" 2500 parts by volume oftechnical pyridine. The

ormation of the dyestufi' starts at once. The dyestuif is purified asdescribed in Example 1. The paste of the trisazodyest-ufi' is dissolvedin warm water, diazotized as in Example 1 and coupled with asodaalkaline solution of 1 (4'-carboxyphenl) -3-methyl 5 pyrazolone(prepared from the hydrazine of the 4- aminobenzoic acid). The dyestuifpurified in the usual manner yields on cotton clear green shades ofexcellent fastness to light.

- Instead of the yrazolone used in the above example in the fth placeone can use other pyrazolone derivatives, for instance l-phenyl-3-methyl-5-pyrazolone derivatives, such as obtained from 2- or 3-aminobenzoic acid or from aniline-2-, or 3- or i-sulfonic acid, orl-phenyl-5-pyrazolone-3-carboxylic acid, or the dipyrazolone obtainedfrom 4.4J-diaminodiphenyl, or the pyrazolone of dehydrothio- .toluidinesulfonic acid, or the pyrazolone of 3-amino-2-hydroxy benzoicacid-5-sulfonic acid, or the pyrazolone obtained in the usual mannerfrom the condensation product from 1 mol p-aminobenzaldehyde and 2 molof ocresotinic acid, corresponding most probably to the formula:

COOH

N-N\ om C-CHa oo-cm or the pyrazolone obtained from2-aminonaphthalene-6-sulfonic acid, or the pyrazolone obtained from2-amino-5-hydroxy naphthalene-7-sulfonic acid. The dyestufi's thusobtained have green shades of similar properties as the dyestuffdescribed above.

E mam/p le 3.-'-7 parts of the sodium salt of the dyestuif of theformula:

, N=N N=N N80; SOaNa I 0 examples and coupled by slowly introducing itin a sodaalkahne solution of 221 parts of acetoaceticacidanilide-4-carbo lic acid The dyestufl' thus obtained has ar propertiesasthe dyestuffs described above.

' Instead of 1-amino-5-acetohydroxynaphthalene-I-sulfonic acid used inthis example I in the third place one can employ with asimilar successthe following compounds which couple in para-position to the aminogroup: 1-amino-5- droxynaphthalene, 1-amin0-5- hydroxynapthalene-G-sulfonic acid, l-amino-8-hydroxynaphthalene-6-sulfonic acid,or

' I the o-acetyl derivatives thereof.

Instead of acetoaceticacid anilide-4-car-' boxylic acid used in theabove example in the v fifth place one can use acetoaceticacid anilide,

ac'etoaceticacid-2-toluidide, acetoaceticacid- 2-chloroanilide,acetoaceticacid4-anisidide,

2o acetoaceticacid- 5 -nitro-4-chloro- 2 -anisidide of the probableformula:

CHLCO-CHl-OO-NH NO;

CHI

di-(acetoacetyl) -tolidide of the most probable formula:

cmoocmoonnpqmco.cm.co.cm H, H.

benzoylaceticacid anilide, etc., or other derivatives of thefl-ketoaldehydes, for instance 1.3-diketohydrindene of the formula:

' o'o 0 v EH! The dyestufis thus obtained yield clear green shades ofexcellent fastness to light.

We wish it to be understood that We claim in this application only thecompounds of the general formula given at the beginning of thespecification, Whereas the compounds of the general formula:

wherein R represents an aromatic residue,

R a residue of the naphthalene series, B, the

residue of a suitable end component, X hydrogen, an alkyl or acidylgroup, and Y h drogen or any monovalent substituent will e claimed in acopending application.

The formulas of the dyestuffs described .65 and claimed herein will bereadily apparent from the following table in which the variouscomponents of our dycstuflt's are listed:

First component First middle component Second middle component Thirdmiddle component Final component (1) i-amino-henzene-2.5-

disulionic acid (2 2-amino-1-methoxyzene-4-suifonic acid (3)3-chlor-1-amino-benzene-fisullonic acid (4) 1-amino-benzene-3- sullonicacid (5) l-amino-benzene-2-4- disulionic acid (6)4-nitro-l-amino-benzene-2-54lisullonic acid (7) 2-naphthylamine-5-7-disullonic acid (8) 2-naphthy1amine-5-7- disulionic acid (9)2-naphthylamine5-7- disullonic acid (10) 1-amino-benzene-2.4-

disullonic acid (11) aniline-2.3.6-trisulionic acid (12)aminobenzene-2.4-

disullonic acid (13) aminobenzene-2.4-

disulionic acid 1-a1nino-naphthalene-7- suiionic acid1-aii1ino-naphthaiene-6- sullonic acid mixture oi the isomeric 6;

and 7-su1ionic aci i-amino nap hthalene l-amino-nap thaiene-7- sulionicacid l-amino-naphthalene i-amino naphthalenel-amino-naphthaiene-fisulionic acid l-amino-naphthaiene-osuii'onic acidl-amino-naphthaiene-fisulfonic acid l-amino-naphthaienei-amino-naphthaiene l-amino-naphthalene Lamina-naphthalene1-amin0-2-ethoxy-6-sulionic acid I-amino-Z-methoxy-naphthalene1-amino-2.7-dimethoxynaphthalene 1-amino-2-naphthydroxy-propionic acid1-amino-2.7-naphthyleneglycollic acid u suli'onic ester of l-amino-2-hydroxy-ethoxy-naphthalene l-amino-Z-ethoxy naphthalene-B-sulionicacid 1-amino-2-ethoxy naphthalene-(i-sulionic acid l-amino-Z-ethoxynaphthalene-fi-sulfonic acid I-amino-S'acet-hYdroxynaphthaieneJ-suifonic801d 1-amino-5-acet-hydroxynaphthalene l-amino-S-acethydroxynaphthalene6 sullonic acid 1-amino8-acethydroxynaphthalene-G-sulfonic acid4'-amino-benzoyl-2-aminofi-hydroxy naphthalene- 7-su1fonic acid4'-amino-benzoyl-2-amino- 5-hydroxy naphthalene- 7-su1ionic acid3-amino-henzoyl-2-amind 5-hydroxy-naghthaiene 7-sulionic aci3-amino-benzoyl-2-amino- 5-hydroxy-na hthalene- 7-suiionic aci3'-amino-benzoyl2-aminofi-hydroxy-naphthalene- 7-sultonic acid 3-aminobenzoyl-2-amino- 5-hydroxy-naphthaiene- 7-sulionic acidmethyl-ketol-sulionic acid methylketoi-sullonic 7 acidmethyl-ketoi-suiionic acid I methyl ketoi sullazone salicylic acidpyrazolone oi the condensation product cl 1 moi oi araamino-benzalde ydeand two mole of orthocresotinic acid pyrazolone ofmminonaplhthalene-fi-suitnnic pyrazolone ol 2-amino-5- hydroxy-nahthalene- 7-sulfonic ac d aceto acetic acid-anilide 4-carboxylic acidaceto acetic acid-anilide 4-carboxylic acid aceto acetic acid-anilide4-carboxylic acid 1.3-dikctohydrindene We claim:

1. As new products the azo dyestufis of the general formula 0X OHwherein R and B represent aromatic residues,

lene series, R at residue 0 component, X hydrogen,

and Y hydrogen or any substituentbeing in a of grayish-green toblack-green, color, easily soluble in water with a blue-green toyellow-green color,. and in con R represents a residue of the naphthafany suitable end an alkyl or acidyl monovalent dry state dark powders toblack centrated sulfuric acid with olive-green color, dyeing cottonclear green shades of excellent fastness to light.

2. As new products the azo dyestufis having probably the formula:

wherein at least one X represents a substituent of .the groiig incluhydroxyl, alkoxyl, or acylo e other s represent hydrogen or any ot ersubstituent, Y and Y, represent hydrogen or a mono'valent residue, and Rthe resi no of any suitable end component, being in a dry state darkwders of grayisheen to black-green to b ack color, easily so uble inwater with a blue-green to 10 yellow-green color, and in concentratedsulfuric acid with olive-green color, dyeing cotltiolll1 clear greenshades of excellent fastness to g t.

3. As new products the azo dyestuffs having probably the formula:

, sea: on

N= N=N sols NmooO rem-o 40 0.11 0.11

- soar ex. on

N= N N==N N=N 2o soar macaw-O7 our 0.1:

wherein X stands for an alkyl group and R stands for a methyl-ketolcompound, which are in a dry state dark powders of grayish-- green toblack-green to black color, easily soluble in water with a blue-green toyellowgreen color, and in concentrated sulfuric acid with olive-greencolor, dyeing cotton clear l I green shades of excellent fastness to liht.

. 4. As a new product the azo dyestu having probably the formula:

' WINFRID HENTRICH.

MAX HARDTMANN.

